Synthesis of unsaturated esters and lactone from butadiene and carbon
dioxide
    1.
    发明授权
    Synthesis of unsaturated esters and lactone from butadiene and carbon dioxide 失效
    从丁二烯和二氧化碳合成不饱和酯和内酯

    公开(公告)号:US4167513A

    公开(公告)日:1979-09-11

    申请号:US939793

    申请日:1978-09-05

    摘要: Octadienyl esters of 2-ethylidene-hepta-3,5-dienoic and 2-vinyl-hepta-3,5-dienoic acids of formula C.sub.8 H.sub.11 COOC.sub.8 H.sub.13 and .delta.-lactone of formula ##STR1## or 2-ethylidene-hepta-6-ene-5-olide, are prepared by reaction of 1,3-butadiene with CO.sub.2 at a temperature comprised between about 20.degree. and 150.degree. C. and at a total pressure between about 10 and 500 atm in the presence of a phosphinic complex of palladium having the formula Pd[P(R).sub.3 ].sub.x, wherein x is an integer from 2 to 4, and (R).sub.3 is a homogeneous or heterogeneous group consisting of alkyls, cycloalkyls having up to 8 carbon atoms and of phenyls, also substituted, in an inert atmosphere.The obtained products are "per se" new and are valuable intermediates for synthesis of chemicals (fungicides, pesticides, etc.) and in particular as effective plasticizers.

    摘要翻译: 式C 8 H 11 COOC 8 H 13的2-亚乙基 - 庚-3,5-二烯酸和2-乙烯基 - 庚-3,5-二烯酸的辛二烯基酯和式(II)的δ-内酯或2-亚乙基 - 七 烯-5-醇通过1,3-二丁烯与CO 2在约20-150℃的温度下反应并在约10-500atm的总压下在次膦酸盐络合物 具有式Pd [P(R)3] x的钯,其中x是2至4的整数,(R)3是由烷基,具有至多8个碳原子的环烷基和苯基组成的均相或异质基团 也在惰性气氛中取代。

    Process for preparing aryl- or heteroarylhexadienoic acids
    2.
    发明授权
    Process for preparing aryl- or heteroarylhexadienoic acids 失效
    制备芳基或杂芳基己二烯酸的方法

    公开(公告)号:US4355168A

    公开(公告)日:1982-10-19

    申请号:US212238

    申请日:1980-12-02

    CPC分类号: C07D333/24 C07C51/353

    摘要: There is disclosed and claimed a process for preparing aryl- and heteroarylhexadienoic acids which is characterized in that an aryl- or heteroarylacetylene having the formula: R--C.tbd.CH, wherein R is an aryl or heteroaryl group, optionally substituted and having in the aggregate up to 20 carbon atoms, is reacted with 3-butenoic acid CH.sub.2 .dbd.CH--CH.sub.2 --COOH, in an alcoholic medium, at temperatures maintained between 50.degree. C. and 120.degree. C., approximately, in the presence of a catalyst selected from among the phosphinic complexes of rhodium having the formulas: III, Rh(PR'.sub.3).sub.n L.sub.m X associated with alkaline salts of carboxylic acids having up to 4 carbon atoms, and IV, Rh(PR'.sub.3).sub.n L.sub.p.sup.+ Y.sup.-, wherein R' is a hydrocarbyl group having up to 12 carbon atoms; "L" is a linear or cyclic olefin selected from among the olefins having from 2 to 10 carbon atoms and the chelating olefins having from 6 to 8 carbon atoms, n is an integer from 1 to 3, m is an integer from 0 to 2 and such that n+m=2 or 3, and p is an integer from 0 to 3 and such that n+p=3 or 4; X is an anion selected from among the haloid anions, preferably the hydrochloric anion, and the anions of carboxylic acids having up to 4 carbon atoms and Y is a sparingly coordinating anion, preferably selected from PF.sub.6.sup.- and BF.sub.4.sup.-.The compounds obtained are used as intermediates for organic syntheses, with particular regard to the so-called "fine chemicals" such as, for example, additives for polymers and paints, plasticizers, and the like.

    摘要翻译: 公开并要求了一种制备芳基 - 和杂芳基己二烯酸的方法,其特征在于具有下式的芳基 - 或杂芳基乙炔:其中R是芳基或杂芳基,其中R是芳基或杂芳基, 20个碳原子与3-丁烯酸CH 2 = CH-CH 2 -COOH在醇的介质中在保持在50℃和120℃之间的温度下反应,大约在存在催化剂的情况下,选自 具有以下结构式的铑的次膦酸络合物:III,Rh(PR'3)nLmX与具有至多4个碳原子的羧酸的碱金属盐,以及IV,Rh(PR'3)nLp + Y-,其中R'为 具有至多12个碳原子的烃基; “L”是选自具有2至10个碳原子的烯烃和具有6至8个碳原子的螯合烯烃,n为1至3的整数的直链或环状烯烃,m为0至2的整数 并且使得n + m = 2或3,并且p是0至3的整数,并且使得n + p = 3或4; X是选自卤素阴离子,优选盐酸阴离子的阴离子和具有至多4个碳原子的羧酸阴离子,Y是一种微量配位阴离子,优选选自PF6-和BF4-。 所得化合物用作有机合成的中间体,特别涉及所谓的“精细化学品”,例如聚合物和油漆的添加剂,增塑剂等。

    Process for the preparation of methyl esters of arylpropionic acids
optically active
    4.
    发明授权
    Process for the preparation of methyl esters of arylpropionic acids optically active 失效
    制备芳基丙酸甲基酯光学活性的方法

    公开(公告)号:US4439618A

    公开(公告)日:1984-03-27

    申请号:US405608

    申请日:1982-08-05

    CPC分类号: C07C59/64 C07C69/612

    摘要: Optically active methyl esters of arylpropionic acids are prepared by reaction of the corresponding vinylaromatic compounds with carbon monoxide and methyl alcohol in the presence of a palladium catalyst system consisting of a palladium compound associated with optically active diphenyl-neomenthylphosphine and with trifluoroacetic acid, at substantially atmospheric pressure and at a temperature comprised between 20.degree. and 80.degree. C. There is dealt with particular regioselective and enantioselective catalysis conditions.The products obtained consist of esters of arylpropionic acids or of the corresponding acids obtainable from them, and are useful intermediates in the synthesis of organic compounds, particularly of pharmaceutical products.

    摘要翻译: 芳基丙酸的光学活性甲基酯是在相当于乙烯基芳族化合物与一氧化碳和甲醇的钯催化剂体系存在下制备的,该钯催化剂体系由与光学活性的二苯基 - 新戊基膦和三氟乙酸相关的钯化合物在大气中 压力和温度在20°C和80°C之间。处理特定的区域选择性和对映选择性催化条件。 获得的产物由芳基丙酸或其可从其获得的相应酸的酯组成,并且是合成有机化合物,特别是药物产品的有用中间体。

    Process for preparing dienoic acids
    5.
    发明授权
    Process for preparing dienoic acids 失效
    二烯酸的制备方法

    公开(公告)号:US4465634A

    公开(公告)日:1984-08-14

    申请号:US333934

    申请日:1981-12-23

    CPC分类号: C07C51/353

    摘要: This invention relates to a process for preparing dienoic acids.In particular, the present invention relates to a catalytic process for preparing octadienoic acids from 3-butenoic acids and butadiene.More particularly the present invention is directed to the preparation of octadienoic acids haing the two double bonds in position 3,6 and 2,6 in respect of the carboxylic carbon, starting from 3-butenoic acids and butadiene in the presence of complex catalysts of Rhodium or of Nickel.

    摘要翻译: 本发明涉及二烯酸的制备方法。 特别地,本发明涉及由3-丁烯酸和丁二烯制备辛二烯酸的催化方法。 更具体地说,本发明涉及在铑络合物催化剂存在下,从3-丁烯酸和丁二烯开始制备相对于羧酸在位置3,6和2,6上的两个双键的辛二烯酸 或镍。